Methylphenyldichlorosilane(MPDS, CH3C6H5 SiC l2) is an important silicone monomer for the synthesis of highperformance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methy...Methylphenyldichlorosilane(MPDS, CH3C6H5 SiC l2) is an important silicone monomer for the synthesis of highperformance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C\Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.展开更多
A semicircular section tubular photoreactor has been constructed, characterized and applied to the treatment of groundwater contaminated with As（V） by means of the SORAS （solar oxidation and removal of arsenic） te...A semicircular section tubular photoreactor has been constructed, characterized and applied to the treatment of groundwater contaminated with As（V） by means of the SORAS （solar oxidation and removal of arsenic） technique, using ferrous and citrate salts. The solar concentrator was built with recyclable waste materials： glass tubes from fluorescent lamps and 6-inch diameter PVC pipes cut in half and covered by aluminum foil. The reactor concentrates solar radiation up to 2.8 times its natural intensity. Batch irradiation experiments followed by controlled agitation （shear rate = 30-33 s^-1; 20 min agitation period） showed that the photoreactor accelerates the formation of settleable floccules （Dp 〉 0.5mm）, compared with a fluorescent lamp glass tube alone and a 2 L PET （polyethylene terephthalate） bottle. Irradiation times necessary for floccule formation in the photoreactor, the fluorescent lamp tube and the PET bottle were 15 min, 25 min and 60 min, respectively. Continuous flow experiments using a photoreactor with a photo-collection area of 0.9 m^2 and a hydraulic retention time （equal to the irradiation time） of 15 rain showed that immediate formation of floccules of good settleability occurs when the solution is subjected to moderate agitation （33 s^-1）. An efficiency of 98.36% for As（V） removal was obtained with a final concentration of 16.5 ktg/L in decanted waters. In accordance to these results, the photoreactor is able to treat approximately 130 L/m^2 within a 5-h period with UVA irradiation intensities of 50-70 W/mE.展开更多
4-Acyl-β-lactams are important synthetic intermediates in both pharmaceutical and organic chemistry. Cis- and trans-4-acyl-β- lactams were synthesized stereoselectively from vicinal diketones via the formation of bu...4-Acyl-β-lactams are important synthetic intermediates in both pharmaceutical and organic chemistry. Cis- and trans-4-acyl-β- lactams were synthesized stereoselectively from vicinal diketones via the formation of bulky and less bulky diimines as key intermediates, respectively. The diimines reacted with acyl chloride in the presence of triethylamine to give rise to the corre- sponding 4-imino-β-lactams, which were further hydrolyzed to afford 4-acyl-β-lactams. The cis- and trans selectivity is de- pended on the steric hindrance of the imine N-substituents. A series of cis-4-acyl-β-lactams were synthesized from vicinal ketoaldehydes via the formation of their monoimines and diimines as intermediates. Pyruvic aldehyde produced cis-4-acetyl-β- lactams and cis-4-formyl-β-lactams, respectively, through the reactions of its monoimine and diimine with acyl chlorides. Phenylglyoxal generated cis-4-benzoyl-β-lactams via its monoaldimine.展开更多
文摘Methylphenyldichlorosilane(MPDS, CH3C6H5 SiC l2) is an important silicone monomer for the synthesis of highperformance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C\Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.
文摘A semicircular section tubular photoreactor has been constructed, characterized and applied to the treatment of groundwater contaminated with As（V） by means of the SORAS （solar oxidation and removal of arsenic） technique, using ferrous and citrate salts. The solar concentrator was built with recyclable waste materials： glass tubes from fluorescent lamps and 6-inch diameter PVC pipes cut in half and covered by aluminum foil. The reactor concentrates solar radiation up to 2.8 times its natural intensity. Batch irradiation experiments followed by controlled agitation （shear rate = 30-33 s^-1; 20 min agitation period） showed that the photoreactor accelerates the formation of settleable floccules （Dp 〉 0.5mm）, compared with a fluorescent lamp glass tube alone and a 2 L PET （polyethylene terephthalate） bottle. Irradiation times necessary for floccule formation in the photoreactor, the fluorescent lamp tube and the PET bottle were 15 min, 25 min and 60 min, respectively. Continuous flow experiments using a photoreactor with a photo-collection area of 0.9 m^2 and a hydraulic retention time （equal to the irradiation time） of 15 rain showed that immediate formation of floccules of good settleability occurs when the solution is subjected to moderate agitation （33 s^-1）. An efficiency of 98.36% for As（V） removal was obtained with a final concentration of 16.5 ktg/L in decanted waters. In accordance to these results, the photoreactor is able to treat approximately 130 L/m^2 within a 5-h period with UVA irradiation intensities of 50-70 W/mE.
基金the support from the National Natural Science Foundation of China (20972013 and 20772005)Beijing Natural Science Foundation (2092022)+1 种基金the Fundamental Research Funds for the Central Universities (ZZ1020)the Doctoral Fund of Ministry of Edu-cation of China (200800100010)
文摘4-Acyl-β-lactams are important synthetic intermediates in both pharmaceutical and organic chemistry. Cis- and trans-4-acyl-β- lactams were synthesized stereoselectively from vicinal diketones via the formation of bulky and less bulky diimines as key intermediates, respectively. The diimines reacted with acyl chloride in the presence of triethylamine to give rise to the corre- sponding 4-imino-β-lactams, which were further hydrolyzed to afford 4-acyl-β-lactams. The cis- and trans selectivity is de- pended on the steric hindrance of the imine N-substituents. A series of cis-4-acyl-β-lactams were synthesized from vicinal ketoaldehydes via the formation of their monoimines and diimines as intermediates. Pyruvic aldehyde produced cis-4-acetyl-β- lactams and cis-4-formyl-β-lactams, respectively, through the reactions of its monoimine and diimine with acyl chlorides. Phenylglyoxal generated cis-4-benzoyl-β-lactams via its monoaldimine.
